CN117142486B - MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural - Google Patents

MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural Download PDF

Info

Publication number
CN117142486B
CN117142486B CN202311120889.2A CN202311120889A CN117142486B CN 117142486 B CN117142486 B CN 117142486B CN 202311120889 A CN202311120889 A CN 202311120889A CN 117142486 B CN117142486 B CN 117142486B
Authority
CN
China
Prior art keywords
molecular sieve
mcm
hydroxymethylfurfural
mww structure
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311120889.2A
Other languages
Chinese (zh)
Other versions
CN117142486A (en
Inventor
巩雁军
肖鹏
曹世伟
李章明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN202311120889.2A priority Critical patent/CN117142486B/en
Publication of CN117142486A publication Critical patent/CN117142486A/en
Application granted granted Critical
Publication of CN117142486B publication Critical patent/CN117142486B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of molecular sieve catalysis, in particular to an MWW structure molecular sieve, a preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural. The method provided by the invention can controllably synthesize the MWW structure molecular sieve by a one-step method under a sodium-free system, even the MWW structure molecular sieve containing metal hetero atoms, thereby simplifying the operation steps and reducing the environmental pollution; the prepared MWW structure molecular sieve containing the metal hetero atom has good structural stability, uniform metal dispersion and controllable content, and the acidity of the molecular sieve is easy to modulate. More importantly, the molecular sieve has high catalytic activity for preparing 5-hydroxymethylfurfural by catalytic conversion of glucose. Experiments show that compared with other molecular sieves with MWW structure, the molecular sieve with the MWW structure prepared by the method provided by the invention has more excellent morphology and crystallinity, and the conversion rate, yield and selectivity of preparing 5-hydroxymethylfurfural by using the molecular sieve as a catalyst are obviously better.

Description

MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural
Technical Field
The invention relates to the field of molecular sieve catalysis, in particular to an MWW structure molecular sieve, a preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural.
Background
It is known that MWW molecular sieves have a specific two-dimensional layered structure and unique pore characteristics, a large external specific surface area, excellent thermal and hydrothermal stability, and adjustable acidity, making them widely used in macromolecular catalytic conversion reactions, and in particular, their own lower diffusion limitations and higher product selectivity have significant advantages in macromolecular catalytic reactions. Among them, MCM-22, MCM-49 and MCM-56 molecular sieves are widely used as important members of the MWW type molecular sieve family.
At present, an inorganic alkali (such as sodium hydroxide and potassium hydroxide) is generally adopted in a molecular sieve synthesis system to form an alkaline environment suitable for crystallization of a molecular sieve, the synthesized molecular sieve is Na or K type molecular sieve, and then the molecular sieve can be converted into a hydrogen type molecular sieve catalyst through multiple steps of ammonia exchange, washing, filtering, roasting and the like; the prepared hydrogen molecular sieve is further uniformly mixed with a metal solution, and then the heteroatom metal-containing molecular sieve catalyst can be prepared through steps such as drying, roasting and the like. The preparation process not only can generate a large amount of ammonia nitrogen sewage or acid-containing wastewater and cause great environmental protection pressure to production enterprises, but also has the problems of complex process, harsh operation conditions, catalyst structure damage, poor dispersibility of metal species and the like.
As patent CN114314607 discloses a method for preparing Na-type MCM-22 molecular sieve and catalytic benzene alkylation reaction thereof, the method uses hexamethyleneimine and morpholine as templates to obtain Na-type MCM-22 molecular sieve, the obtained Na-type MCM-22 molecular sieve also needs to undergo the steps of complex ammonia exchange, washing, roasting, etc. to prepare H-type MCM-22, the method is time-consuming and laborious, and the produced ammonia nitrogen wastewater is extremely unfavorable for environment-friendly development.
Patent CN112429745 discloses a preparation method of an H-type MCM-22 molecular sieve, and the preparation method needs the following steps: firstly, piperidine or hexamethyleneimine is used as a template agent to prepare boron-containing MCM-22 molecular sieve raw powder, then MCM-22 molecular sieve is subjected to boron removal treatment, and finally MCM-22 molecular sieve subjected to boron removal treatment is subjected to aluminum supplementing treatment to obtain the H-type MCM-22 molecular sieve, and the preparation method is complicated and tedious in preparation steps, strict in operation requirement and high in cost, and is unfavorable for industrial production although the H-type MCM-22 molecular sieve is obtained.
The patent CN104437592 discloses a silicon aluminum molecular sieve catalyst with MWW structure and a preparation method thereof, the preparation method firstly takes non-equivalent tetraalkylammonium cations as a template agent to synthesize a Na-type MWW molecular sieve, the obtained Na-type MWW molecular sieve is subjected to constant temperature (150-600 ℃) heat treatment for 1-3 hours under the air atmosphere, then is subjected to acid washing treatment, and then is subjected to exchange treatment with ammonium nitrate solution, the obtained molecular sieve raw powder is subjected to kneading, forming, ageing, drying and roasting to obtain a catalyst body, and finally the catalyst body is impregnated with a modified impregnating solution containing VIII group elements for 12-24 hours, and then is dried and roasted to obtain the target molecular sieve, so that the process steps are complicated and the preparation time is long.
In summary, the existing MWW molecular sieve has the problems of complex preparation process, difficult operation, time and labor consumption, high template toxicity, serious environmental pollution, structural damage, poor metal dispersibility and the like.
5-Hydroxymethylfurfural is an important biomass-based platform compound having a structure of multiple functional groups including one furan ring, one aldehyde group and one hydroxymethyl group, and thus can be used for preparing high added value chemicals through various reactions such as hydrogenation, oxidation, halogenation, polymerization, hydrolysis and the like. At present, the preparation of 5-hydroxymethyl furfural mainly adopts homogeneous catalysis, and the adopted organic acid or inorganic acid catalyst has the problems of difficult separation, poor recycling property, serious equipment corrosion and the like, and is unfavorable for green sustainable development. In contrast, solid acid catalysts are effective in avoiding these problems. However, the traditional solid acid catalyst has the problems of low yield, poor selectivity and the like of the 5-hydroxymethylfurfural, and greatly limits the application of the solid acid catalyst.
For example, min et al (Min H.et al.Single-step preparation of zinco-and aluminosilicate delaminated MWW layers for the catalytic conversion of glucose.Green Chem.,2021,23,9489.) prepared MWW molecular sieves containing zinc and aluminum by a one-step hydrothermal treatment process using a B-MWW molecular sieve (hexamethyleneimine as a template) as a precursor, and used for catalytic conversion of glucose to prepare 5-hydroxymethylfurfural, the highest yield of 5-hydroxymethylfurfural was only 40% although the catalytic activity was higher than SnAl-BEA molecular sieves.
Patent CN112625012 discloses a method for preparing 5-hydroxymethylfurfural by catalyzing glucose with a tin modified molecular sieve catalyst, wherein a tin-containing SAPO-34 molecular sieve is prepared by an immersion method, and the maximum yield of 5-hydroxymethylfurfural is close to 60% in the reaction of preparing 5-hydroxymethylfurfural by catalytic conversion of glucose.
Patent CN108440463 discloses a method for preparing 5-hydroxymethylfurfural by using a supported metal molecular sieve catalyst, wherein the supported metal molecular sieve catalyst is prepared by a metal post-modification method, and the maximum yield of 5-hydroxymethylfurfural is close to 60% in the reaction of preparing 5-hydroxymethylfurfural by catalytic conversion of glucose.
Therefore, the development of a green and efficient solid acid catalyst has important practical significance for the efficient utilization of biomass resources.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an MWW structure molecular sieve, a preparation method thereof and an application thereof in preparation of 5-hydroxymethylfurfural, wherein the method provided by the present invention can be used for further synthesis in a sodium-free system to obtain the MWW structure molecular sieve, in particular, a hydrogen-type MWW structure molecular sieve, even a hydrogen-type MWW structure molecular sieve containing metal heteroatoms, which has high catalytic activity and catalytic selectivity in the reaction of preparing 5-hydroxymethylfurfural by catalytic conversion of glucose.
The invention provides a preparation method of an MWW structure molecular sieve, which comprises the following steps:
s1) mixing raw materials comprising a silicon source, an alkali source, an aluminum source, a template agent and water to obtain precursor gel; the template agent is selected from cyclohexylamine, hexamethyleneimine or piperidine; the alkali source is selected from one or more of ammonia water or urea;
S2) heating and dynamically crystallizing the precursor gel obtained in the step S1), and washing, suction filtering, drying and roasting the obtained product to obtain the MWW structure molecular sieve.
The MWW structure molecular sieve prepared by the application is a hydrogen type MWW structure molecular sieve. The inventor creatively discovers that ammonia water or urea is used as an alkali source, so that the molecular sieve with the hydrogen MWW structure can be obtained through the next synthesis of a sodium-free system, the steps of ammonia exchange, washing, suction filtration, drying, roasting and the like are avoided, the preparation process is optimized, the environmental pollution is reduced, the structural damage of the molecular sieve is reduced, metal heteroatoms can be simultaneously introduced on the basis of one-step synthesis to improve the acidity of the molecular sieve L, and meanwhile, the ratio of L acid to B acid is modulated, so that the catalytic activity is further improved; and the prepared MWW structure molecular sieve is used as a catalyst in the reaction of preparing 5-hydroxymethylfurfural by catalytic conversion of glucose, and has ultrahigh catalytic activity and long service life compared with molecular sieves with other structures.
Firstly, raw materials comprising a silicon source, an alkali source, an aluminum source, a template agent and water are mixed to obtain precursor gel. Specifically, after mixing an aluminum source and water, sequentially adding an alkali source, a template agent and a silicon source into the mixture, and mixing the mixture to obtain precursor gel. In certain embodiments of the invention, the precursor gel is obtained by mixing an aluminum source with water, then sequentially adding an alkali source, a template agent and a silicon source, and stirring and mixing at 60 ℃ for 6-12 hours.
The molar ratio of SiO 2, alkali source, al 2O3, template agent and water in the precursor gel obtained by the invention is 1: (1-3.5): (0.005-0.5): (0.1-1.0): (15-50). If the alkali source is calculated by hydroxyl contained, the mol ratio of SiO 2、OH-、Al2O3, template agent and water in the precursor gel obtained by the invention is 1: (0.5-2.0): (0.005-0.5): (0.1-1.0): (15-50). The silicon source is one or more selected from white carbon black, ammonia silica sol, coarse pore silica gel, silicic acid and tetraethoxysilane; the aluminum source is selected from one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum oxide monohydrate. The template agent is selected from cyclohexylamine, hexamethyleneimine or piperidine, preferably cyclohexylamine, and compared with the template agent (hexamethyleneimine or piperidine) required for synthesizing the conventional MWW molecular sieve at present, the cyclohexylamine has the advantages of low price, low toxicity and the like, and can also be used as the template agent required for synthesizing the MWW structure molecular sieve.
The silicon source of the invention can also be a silicon source containing metal ions; the metal ion is selected from one or more of chromium ion, copper ion, zinc ion, manganese ion and iron ion. By using a silicon source containing metal ions, the present invention is capable of synthesizing not only a hydrogen form MWW structured molecular sieve in one step, more specifically, a hydrogen form MWW structured molecular sieve containing metal hetero atoms in one step. When the silicon source is a silicon source containing metal ions, the raw material further comprises a metal complexing agent, wherein the metal complexing agent is selected from ethylenediamine or triethylamine. The molar ratio of SiO 2, alkali source, al 2O3, template agent, metal complexing agent and water in the gel obtained by the invention is 1: (1-3.5): (0.005-0.5): (0.1-1.0): (0.01-0.2): (15-50); if the alkali source is calculated by hydroxyl contained, the mol ratio of SiO 2、OH-、Al2O3, template agent and water in the precursor gel obtained by the invention is 1: (0.5-2.0): (0.005-0.5): (0.1-1.0): (0.01-0.2): (15-50); and the molar ratio of metal ions to SiO 2 in the obtained gel is more than 0 and less than or equal to 0.05.
After the precursor gel is obtained, the obtained precursor gel is heated and dynamically crystallized, and the MWW structure molecular sieve is obtained after washing, suction filtration, drying and roasting of the obtained product. Specifically, the method comprises the steps of heating, stirring and ageing the obtained precursor gel, heating and dynamically crystallizing, washing, suction filtering, drying and roasting the obtained product to obtain the MWW structure molecular sieve. More specifically, the method comprises the steps of heating, stirring and ageing the obtained precursor gel, carrying out heating dynamic crystallization, washing, filtering and drying the product obtained by the hydrothermal dynamic crystallization, and roasting for 5-7 h at 500-600 ℃ to obtain the MWW structure molecular sieve.
The container for heating dynamic crystallization rotates by taking the horizontal axis as a rotating shaft. In certain embodiments of the invention, the thermal dynamic crystallization process is performed in an autoclave equipped with a polytetrafluoroethylene liner. The temperature of the heating dynamic crystallization is 140-180 ℃, preferably 150-160 ℃; the time for heating dynamic crystallization is 48-144 h, preferably 60-120 h.
The invention provides a preparation method of the silicon source containing metal ions, which comprises the following steps: and mixing and calcining the silicon source and the metal salt to obtain the silicon source containing metal ions, which is also called as a metal-silicon composite raw material. Specifically, the silicon source and the metal salt are mixed, dried, and a solid sample obtained after drying is ground and then calcined to obtain the silicon source containing metal ions. The metal salt is one or more selected from chromium salt, copper salt, zinc salt, manganese salt and ferric salt; the silicon source is one or more selected from white carbon black, ammonia silica sol, coarse pore silica gel, silicic acid and tetraethoxysilane. The invention mixes the metal salt and the silicon source to form a mixture, and the molar ratio of the metal ion to SiO 2 in the formed mixture is more than 0 and less than or equal to 0.05 calculated by the metal ion and SiO 2. The calcination temperature is 450-650 ℃, and the calcination time is 3-6 h, preferably 4-5 h.
In certain embodiments of the invention, the silicon source and the metal salt are mixed and ultrasonically stirred for 2-5 hours, dried at 80-120 ℃, and the solid sample obtained after drying is ground for 6-24 hours and then calcined, so that the silicon source containing the metal ions is obtained. Preferably, the silicon source and the metal salt are mixed and ultrasonically stirred for 2-5 hours, dried at the temperature of 90-110 ℃, and the solid sample obtained after drying is ground for 8-16 hours and then calcined, so that the silicon source containing the metal ions is obtained. In certain embodiments of the invention, the milling is ball milling or mortar milling.
The invention provides an MWW structure molecular sieve, which is prepared by the preparation method. In the invention, if the silicon source containing metal ions is adopted to prepare the MWW structure molecular sieve, the MWW structure molecular sieve is the MWW structure molecular sieve containing metal hetero atoms. In certain embodiments of the present invention, the MWW-structured molecular sieve of the present invention comprises an MCM-22 molecular sieve, an MCM-49 molecular sieve, or an MCM-56 molecular sieve. The MWW structure molecular sieve provided by the invention can be used as a catalyst in the reaction of preparing 5-hydroxymethylfurfural by catalytic conversion of glucose.
The invention also provides an application of the MWW structure molecular sieve in preparing 5-hydroxymethylfurfural, and particularly provides a preparation method of 5-hydroxymethylfurfural, which comprises the following steps: under the atmosphere of protective gas, mixing glucose, an organic solvent, sodium chloride, a catalyst and water to perform a glucose catalytic conversion reaction to obtain 5-hydroxymethylfurfural; the catalyst is the MWW structure molecular sieve.
Glucose, an organic solvent, sodium chloride, a catalyst and water are taken as feed materials to be placed in a reactor under the atmosphere of protective gas, and 5-hydroxymethylfurfural is obtained under the condition of catalytic conversion reaction of glucose. Specifically, glucose, an organic solvent, sodium chloride, a catalyst and water are taken as feed materials to be placed in a reactor, protective gas is introduced into the reactor, and glucose catalytic conversion reaction conditions are set, and the 5-hydroxymethylfurfural is obtained by reaction under the reaction conditions. The catalytic conversion reaction of glucose according to the present invention was carried out under intermittent stirring at a rate of 500rpm. The mass ratio of glucose, organic solvent, sodium chloride, catalyst and water is (0.05-0.2): (4-10): (0.2-0.5): (0.01-0.03): (1-4). The temperature of the catalytic conversion reaction of the glucose is 160-200 ℃, preferably 170-180 ℃; the time of the glucose catalytic conversion reaction is 0.25 to 8 hours, preferably 2 to 4 hours. The pressure of the catalytic conversion reaction of glucose is 0.5 MPa-2 MPa, preferably 1 MPa-1.5 MPa. The organic solvent is one or more selected from isopropanol, dimethyl sulfoxide, tetrahydrofuran and gamma-valerolactone. The shielding gas atmosphere in the present invention is an argon atmosphere or a nitrogen atmosphere, preferably an argon atmosphere.
The invention provides an MWW structure molecular sieve, a preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural. The preparation method of the MWW structure molecular sieve provided by the invention can directly and controllably synthesize the sodium-free hydrogen-type MWW structure molecular sieve by using cyclohexylamine, hexamethyleneimine or piperidine and the like as a template agent, particularly using low-toxicity and low-cost cyclohexylamine as the template agent in a one-step method under a sodium-free system, so that the operation steps are simplified, and the environmental pollution is reduced; the prepared MWW structure molecular sieve has good structural stability, controllable metal content and uniform metal dispersion, and the acidity of the molecular sieve is easy to modulate. The MWW structure molecular sieve has high catalytic activity for preparing 5-hydroxymethylfurfural through catalytic conversion of glucose. Experiments show that compared with other molecular sieves with MWW structure, the molecular sieve with the MWW structure prepared by the method provided by the invention has more excellent morphology and crystallinity, and the conversion rate, yield and selectivity of preparing 5-hydroxymethylfurfural by using the molecular sieve as a catalyst are obviously better.
Compared with the prior art, the preparation method of the MWW structure molecular sieve provided by the invention has the advantages that the hydrogen MWW structure molecular sieve is directly synthesized by a sodium-free system one-step method, the complex post-treatment process is not needed, the operation steps are simplified, the cost is reduced, the environment is protected, sodium and potassium plasmas are firstly introduced when the hydrogen MWW structure molecular sieve is synthesized in the prior art, and a great amount of ammonium salts are needed to exchange the sodium and potassium plasmas in the subsequent treatment process, so that the serious ammonia nitrogen pollution problem is generated; meanwhile, the invention introduces a plurality of metal species by adopting a one-step preparation method, the prepared MWW structure molecular sieve containing hetero atoms has a stable framework structure, the content of the metal species in the molecular sieve is controllable, the dispersibility is good, meanwhile, the acidity of the molecular sieve is modulated, and the catalytic activity of the molecular sieve is greatly improved. Meanwhile, the MWW structure molecular sieve prepared by the method provided by the invention has ultrahigh catalytic activity and long service life in the reaction of preparing 5-hydroxymethylfurfural by glucose catalytic conversion. In conclusion, the technical scheme of the invention has wide application prospect.
Drawings
FIG. 1 is an SEM image of a sodium-free Cu-MCM-22 molecular sieve prepared according to example 1;
FIG. 2 is an XRD spectrum of a sodium-free Cu-MCM-22 molecular sieve prepared in example 1;
FIG. 3 is an SEM image of a sodium free Cu-MCM-49 molecular sieve prepared according to example 2;
FIG. 4 is an XRD pattern of a sodium-free Cu-MCM-49 molecular sieve prepared in example 2;
FIG. 5 is an SEM image of a sodium-free Cu-MCM-56 molecular sieve prepared according to example 3;
FIG. 6 is an XRD pattern of a sodium-free Cu-MCM-56 molecular sieve prepared in example 3;
FIG. 7 is an SEM image of a sodium free Cr-MCM-56 molecular sieve prepared according to example 4;
FIG. 8 is an XRD pattern of the sodium-free Cr-MCM-56 molecular sieve prepared in example 4;
FIG. 9 is an SEM image of a sodium free Cr-MCM-56 molecular sieve prepared according to example 5;
FIG. 10 is an XRD pattern of the sodium-free Cr-MCM-56 molecular sieve prepared in example 5;
FIG. 11 is an SEM image of a post-modified Cu-MCM-22 molecular sieve prepared according to comparative example 1;
FIG. 12 is an XRD pattern of the post-modified Cu-MCM-22 molecular sieve prepared in comparative example 1;
FIG. 13 is an SEM image of a post-modified Cr-MCM-56 molecular sieve prepared according to comparative example 2;
FIG. 14 is an XRD pattern of the post-modified Cr-MCM-56 molecular sieve prepared in comparative example 2;
FIG. 15 is an SEM image of a sodium-free Cu-Beta molecular sieve prepared according to comparative example 3;
FIG. 16 is an XRD spectrum of a sodium-free Cu-Beta molecular sieve prepared in comparative example 3;
FIG. 17 is an SEM image of a sodium free Cr-ZSM-5 molecular sieve prepared according to comparative example 4;
FIG. 18 is an XRD spectrum of the sodium-free Cr-ZSM-5 molecular sieve prepared in comparative example 4.
Detailed Description
The invention discloses an MWW structure molecular sieve, a preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
Example 1
Preparation of Cu-Si composite raw material, weighing 7.5g of ammonia silica sol with concentration of 40wt% and 0.3g of copper nitrate, mixing, mechanically stirring for 5h, drying the mixture at 100 ℃ for 12h to obtain a solid sample, grinding the solid sample for 12h by a mortar, and roasting at 550 ℃ for 5h to prepare the Cu-Si composite raw material.
Weighing 0.4g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 20g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 3g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 2g of cyclohexylamine into the beaker, and stirring for half an hour to obtain a uniform mixture; 0.25g of ethylenediamine is weighed and dripped into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cu-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue in a water bath at 60 ℃ for 10 hours, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and crystallizing the reaction kettle at 150 ℃ and a rotating speed of 70rpm for 72 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cu-MCM-22 molecular sieve.
SEM images and XRD patterns of the sodium-free Cu-MCM-22 molecular sieve prepared in the example are obtained, the results are shown in figures 1-2, figure 1 is an SEM image of the sodium-free Cu-MCM-22 molecular sieve prepared in the example 1, and figure 2 is an XRD pattern of the sodium-free Cu-MCM-22 molecular sieve prepared in the example 1. As can be seen from fig. 1, the morphology of the sodium-free Cu-MCM-22 molecular sieve prepared in this example is a thin layer stack morphology; as can be seen from FIG. 2, the sodium-free Cu-MCM-22 molecular sieve prepared in this example is a pure phase MCM-22 molecular sieve.
Example 2
Preparing a Cu-Si composite raw material, weighing 3g of coarse pore silica gel and 0.4g of copper nitrate, mixing, stirring for 5 hours to obtain a solid sample, grinding the solid sample for 8 hours by a ball mill, and roasting at 550 ℃ for 4 hours to prepare the Cu-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 20g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 4g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 2.5g of cyclohexylamine into the beaker, and stirring for half an hour to obtain a uniform mixture; 0.3g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cu-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue in a water bath at 60 ℃ for 8 hours, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and crystallizing the reaction kettle at 170 ℃ and a rotating speed of 80rpm for 120 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cu-MCM-49 molecular sieve.
SEM images and XRD patterns of the sodium-free Cu-MCM-49 molecular sieve prepared in this example were obtained, and the results are shown in FIGS. 3 to 4, wherein FIG. 3 is an SEM image of the sodium-free Cu-MCM-49 molecular sieve prepared in example 2, and FIG. 4 is an XRD pattern of the sodium-free Cu-MCM-49 molecular sieve prepared in example 2. As can be seen from fig. 3, the morphology of the sodium-free Cu-MCM-49 molecular sieve prepared in this example is a thin layer uniform distribution morphology; as can be seen from FIG. 4, the sodium-free Cu-MCM-49 molecular sieve prepared in this example is a pure phase MCM-49 molecular sieve.
Example 3
Preparation of Cu-Si composite raw material, weighing 7.5g of ammonia silica sol with concentration of 40wt% and 0.4g of copper nitrate, mixing, mechanically stirring for 5h, drying the mixture at 90 ℃ for 12h to obtain a solid sample, grinding the solid sample for 12h through a ball mill, and roasting at 550 ℃ for 6 h to prepare the Cu-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 25g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 2g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 2.0g of cyclohexylamine into the beaker, stirring and aging for half an hour to obtain a uniform mixture; 0.3g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cu-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue in a water bath at 60 ℃ for 6 hours, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and crystallizing the reaction kettle for 48 hours at 140 ℃ and 50 rpm; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cu-MCM-56 molecular sieve.
SEM images and XRD patterns of the sodium-free Cu-MCM-56 molecular sieve prepared in the example are obtained, the results are shown in figures 5-6, figure 5 is an SEM image of the sodium-free Cu-MCM-56 molecular sieve prepared in the example 3, and figure 6 is an XRD pattern of the sodium-free Cu-MCM-56 molecular sieve prepared in the example 3. As can be seen from fig. 5, the morphology of the sodium-free Cu-MCM-56 molecular sieve prepared in this example is a thin layer aggregation morphology; as can be seen from FIG. 6, the sodium-free Cu-MCM-56 molecular sieve prepared in this example is a pure phase MCM-56 molecular sieve.
Example 4
Preparation of Cr-Si composite raw material, weighing 7.5g of ammonia silica sol with concentration of 40wt% and 0.3g of chromium nitrate, mixing, mechanically stirring for 5h, drying the mixture at 100 ℃ for 12h to obtain a solid sample, grinding the solid sample for 10h by a ball mill, and roasting at 550 ℃ for 5h to prepare the Cr-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 25g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 3g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 1.5g of cyclohexylamine into the beaker, stirring and aging for half an hour to obtain a uniform mixture; 0.2g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cr-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue in a water bath at 60 ℃ for 10 hours, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and crystallizing the reaction kettle at 150 ℃ and a rotating speed of 70rpm for 108 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cr-MCM-56 molecular sieve.
SEM images and XRD patterns of the sodium-free Cr-MCM-56 molecular sieves prepared in this example were obtained, and the results are shown in FIGS. 7 to 8, wherein FIG. 7 is an SEM image of the sodium-free Cr-MCM-56 molecular sieves prepared in example 4, and FIG. 8 is an XRD pattern of the sodium-free Cr-MCM-56 molecular sieves prepared in example 4. As can be seen from FIG. 7, the morphology of the sodium-free Cr-MCM-56 molecular sieve prepared in the embodiment is a thin layer aggregation spherical morphology, and the particle size of the spheres is about 3-4 μm; as can be seen from FIG. 8, the sodium-free Cr-MCM-56 molecular sieve prepared in this example is a pure phase MCM-56 molecular sieve.
Example 5
Preparing Cr-Si composite raw material, weighing 3g of coarse pore silica gel and 0.4g of chromium nitrate, uniformly mixing to obtain a solid sample, grinding the solid sample for 8 hours by a ball mill, and roasting at 550 ℃ for 6 hours to prepare the Cr-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 20g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 2g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 2.0g of cyclohexylamine into the beaker, stirring and aging for half an hour to obtain a uniform mixture; 0.3g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cr-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue in a water bath at 60 ℃ for 12 hours, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and crystallizing the reaction kettle at 150 ℃ and a rotating speed of 70rpm for 60 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cr-MCM-56 molecular sieve.
SEM images and XRD patterns of the sodium-free Cr-MCM-56 molecular sieves prepared in this example were obtained, and the results are shown in FIGS. 9 to 10, wherein FIG. 9 is an SEM image of the sodium-free Cr-MCM-56 molecular sieves prepared in example 5, and FIG. 10 is an XRD pattern of the sodium-free Cr-MCM-56 molecular sieves prepared in example 5. As can be seen from FIG. 9, the morphology of the sodium-free Cr-MCM-56 molecular sieve prepared in the embodiment is a thin layer aggregation spherical morphology, and the particle size of the spheres is about 2-3 mu m; as can be seen from FIG. 10, the sodium-free Cr-MCM-56 molecular sieve prepared in this example is a pure phase MCM-56 molecular sieve.
Comparative example 1
Mixing 7.5g of silica sol with the concentration of 40wt%, 0.2g of sodium aluminate, 0.2g of sodium hydroxide, 15g of deionized water and 2.5g of hexamethyleneimine to form a mixture, stirring the mixture at room temperature for 6 hours to form a mixed gel, carrying out hydrothermal dynamic crystallization on the mixed gel at 150 ℃ for 72 hours, and washing, filtering and drying the obtained product to obtain the Na-type MCM-22 molecular sieve; fully stirring the synthesized Na-type MCM-22 molecular sieve and NH 4 Cl solution of 1 mol.L -1 (the mass ratio is 1:10) for 2 hours at a water bath of 90 ℃, namely carrying out ammonium exchange, washing with deionized water after the exchange is finished, carrying out suction filtration until the pH value is close to neutral, putting a filter cake into a baking oven for drying for 12 hours, and roasting for 6 hours at 550 ℃, wherein the steps are repeated twice to obtain the hydrogen-type MCM-22 molecular sieve; mixing the hydrogen type MCM-22 molecular sieve with copper nitrate solution, stirring for 2 hours at 80 ℃, drying, and roasting for 6 hours at 550 ℃ to obtain the post-modified Cu-MCM-22 molecular sieve.
SEM images and XRD patterns of the post-modified Cu-MCM-22 molecular sieve prepared in this comparative example were obtained, and the results are shown in FIGS. 11 to 12, wherein FIG. 11 is an SEM image of the post-modified Cu-MCM-22 molecular sieve prepared in comparative example 1, and FIG. 12 is an XRD pattern of the post-modified Cu-MCM-22 molecular sieve prepared in comparative example 1. As can be seen from fig. 11, the morphology of the post-modified Cu-MCM-22 molecular sieve prepared in this comparative example is a thin layer uniform distribution morphology; as can be seen from FIG. 12, the post-modified Cu-MCM-22 molecular sieve prepared in this comparative example is a pure phase MCM-22 molecular sieve.
Comparative example 2
Mixing 7.5g of silica sol with the concentration of 40wt%, 0.2g of sodium aluminate, 0.2g of sodium hydroxide, 15g of deionized water and 1.0g of hexamethyleneimine to form a mixture, stirring the mixture at room temperature for 6 hours to form a mixed gel, carrying out hydrothermal dynamic crystallization on the mixed gel at 140 ℃ for 60 hours, and washing, filtering and drying the obtained product to obtain the Na-type MCM-56 molecular sieve; fully stirring the synthesized Na-type MCM-56 molecular sieve and NH 4 Cl solution of 1 mol.L -1 (the mass ratio is 1:10) for 2 hours at a water bath of 90 ℃, namely carrying out ammonium exchange, washing with deionized water after the exchange is finished, carrying out suction filtration until the pH value is close to neutral, putting a filter cake into a baking oven for drying for 12 hours, and roasting for 6 hours at 550 ℃, wherein the steps are repeated twice to obtain the hydrogen-type MCM-56 molecular sieve; mixing the hydrogen type MCM-56 molecular sieve with chromium nitrate solution, stirring for 2 hours at 80 ℃, drying, and roasting for 6 hours at 550 ℃ to obtain the post-modified Cr-MCM-56 molecular sieve.
SEM images and XRD patterns of the post-modified Cr-MCM-56 molecular sieves prepared in this comparative example were obtained, and the results are shown in FIGS. 13 to 14, wherein FIG. 13 is an SEM image of the post-modified Cr-MCM-56 molecular sieves prepared in comparative example 2, and FIG. 14 is an XRD pattern of the post-modified Cr-MCM-56 molecular sieves prepared in comparative example 2. As can be seen from FIG. 13, the morphology of the post-modified Cr-MCM-56 molecular sieve prepared in the comparative example is a thin layer aggregated spherical morphology, and the particle size of the spheres is about 2-3 μm; as can be seen from FIG. 14, the post-modified Cr-MCM-56 molecular sieve prepared by the comparative example is a pure phase MCM-56 molecular sieve.
Comparative example 3
Preparation of Cu-Si composite raw material, weighing 7.5g of ammonia silica sol with concentration of 40wt% and 0.3g of copper nitrate, mixing, mechanically stirring for 5h, drying the mixture at 90 ℃ for 12h to obtain a solid sample, grinding the solid sample for 12h through a ball mill, and roasting at 550 ℃ for 6 h to prepare the Cu-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 8g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 4g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 5g of tetraethylammonium hydroxide solution into the beaker, stirring and aging for half an hour to obtain a uniform mixture; 0.2g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cu-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue for 6 hours at room temperature, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and carrying out static crystallization on the reaction kettle at 140 ℃ for 96 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cu-Beta molecular sieve.
The Cu-Beta molecular sieve prepared in this comparative example was obtained by the preparation method of the heteroatom molecular sieve prepared in one step by a sodium-free system, the SEM images and XRD spectrogram results are shown in FIGS. 15 to 16, FIG. 15 is an SEM image of the sodium-free Cu-Beta molecular sieve prepared in comparative example 3, and FIG. 16 is an XRD spectrogram of the sodium-free Cu-Beta molecular sieve prepared in comparative example 3. As can be seen from fig. 15, the Cu-Beta molecular sieve prepared in this comparative example exhibits a crystal grain aggregation morphology; as can be seen from FIG. 16, the crystallinity of the Cu-Beta molecular sieve prepared in the comparative example is relatively low, which indicates that the one-step synthesis of the heteroatom Beta molecular sieve by the sodium-free system has poor effect.
Comparative example 4
Preparing Cr-Si composite raw material, weighing 3g of coarse pore silica gel and 0.4g of chromium nitrate, uniformly mixing to obtain a solid sample, grinding the solid sample for 8 hours by a ball mill, and roasting at 550 ℃ for 6 hours to prepare the Cr-Si composite raw material.
Weighing 0.6g of aluminum sulfate octadecanoate (Al 2(SO4)3·18H2 O) and placing in a beaker, weighing 10g of deionized water and aluminum sulfate in the beaker, stirring and mixing uniformly, dropwise adding 3g of ammonia water (NH 3·H2 O) with the concentration of 28wt% into the beaker, dripping 1.2g of tetrapropylammonium bromide solution into the beaker, stirring and aging for half an hour to obtain a uniform mixture; 0.2g of ethylenediamine is weighed and added dropwise into the mixture, and the mixture is stirred for half an hour; finally, mixing the prepared Cr-Si composite raw material with the mixture in the beaker to obtain mixed glue; stirring and ageing the mixed glue for 5 hours at room temperature, adding the aged mixed glue into a polytetrafluoroethylene reaction kettle, and carrying out static crystallization on the reaction kettle at 140 ℃ for 96 hours; after the reaction is finished, the product is washed, filtered and dried and is roasted for 6 hours at 550 ℃ to obtain the sodium-free Cr-ZSM-5 molecular sieve.
The Cr-ZSM-5 molecular sieve prepared in this comparative example was obtained by the preparation method of the heteroatom molecular sieve prepared in one step by a sodium-free system, the SEM images and XRD spectrum results are shown in FIGS. 17 to 18, FIG. 17 is an SEM image of the sodium-free Cr-ZSM-5 molecular sieve prepared in comparative example 4, and FIG. 18 is an XRD spectrum of the sodium-free Cr-ZSM-5 molecular sieve prepared in comparative example 4. As can be seen from fig. 17, the Cr-ZSM-5 molecular sieve prepared in this comparative example exhibits a spherical morphology; as can be seen from FIG. 18, the Cr-ZSM-5 molecular sieve prepared in this comparative example is a pure phase ZSM-5 molecular sieve.
The reaction steps for preparing 5-hydroxymethylfurfural by catalytic conversion of glucose are as follows: placing 0.1g of glucose, 0.03g of catalyst, 0.25g of sodium chloride, 2g of ultrapure water and 6g of tetrahydrofuran into a micro reaction kettle; the catalyst adopts the molecular sieves prepared in the examples 1-5 and the comparative examples 1-4 respectively, and the molecular sieves are roasted for 6 hours at 550 ℃ before the reaction; argon is introduced, and the pressure value is regulated to be 1.5MPa; setting the stirring speed to be 500rpm, the heating speed to be 5 ℃/min, and starting timing when the temperature reaches 180 ℃; after 2h of reaction, stopping heating, cooling the reaction kettle to room temperature, obtaining a liquid product through centrifugation, and finally analyzing the liquid product by using a liquid chromatography detector.
The product is detected by liquid chromatography, and the detection method is as follows: glucose was detected using an NH 2 column and a differential reflectance detector (RID), the mobile phase was a mixed solution of acetonitrile and water (acetonitrile: water=8:2), the flow rate was 1ml/min, and the column temperature was 40 ℃; HMF was detected using InertSustain C (5 μm,150nm x 4.6 mm) column and diode array detector (SPD, wavelength 280 nm) with a mobile phase of a mixed solution of acetonitrile and water (acetonitrile: water=2:8), flow rate of 1mL/min, column temperature of 40 ℃.
The glucose conversion, HMF yield and HMF selectivity were calculated by the following formulas 1 to 3, respectively, and the reaction results of the catalytic conversion of glucose to 5-hydroxymethylfurfural are shown in table 1:
TABLE 1
Examples Glucose conversion HMF yield HMF selectivity
Example 1 88.7％ 70.6％ 79.6％
Example 2 86.6％ 72.4％ 83.6％
Example 3 87.3％ 75.4％ 86.4％
Example 4 84.6％ 71.6％ 84.6％
Example 5 91.5％ 79.9％ 87.3％
Comparative example 1 79.6％ 50.5％ 63.4％
Comparative example 2 77.4％ 51.9％ 67.1％
Comparative example 3 76.1％ 45.4％ 59.7％
Comparative example 4 75.8％ 44.8％ 59.1％
As can be seen from Table 1, the catalytic performance of the hydrogen MWW molecular sieve containing metal hetero atoms prepared by the method is obviously better than that of the hydrogen MWW molecular sieve containing metal hetero atoms prepared by the traditional method, and only the MWW molecular sieve has particularly obvious catalytic performance improving effect by adopting the method, but no improving effect is achieved for molecular sieves with other structures such as ZSM-5 molecular sieves or Beta molecular sieves.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (6)

1. The preparation method of the 5-hydroxymethylfurfural is characterized by comprising the following steps of:
under the atmosphere of protective gas, mixing glucose, an organic solvent, sodium chloride, a catalyst and water to perform a glucose catalytic conversion reaction to obtain 5-hydroxymethylfurfural;
the catalyst is MWW structure molecular sieve, and the preparation method comprises the following steps:
S1) mixing raw materials comprising a silicon source containing metal ions, an alkali source, an aluminum source, a template agent, a metal complexing agent and water to obtain precursor gel; the template agent is selected from cyclohexylamine, hexamethyleneimine or piperidine; the alkali source is selected from one or more of ammonia water or urea; the metal ions are selected from one or more of chromium ions, copper ions, zinc ions, manganese ions and iron ions;
The molar ratio of SiO 2, alkali source, al 2O3, template agent, metal complexing agent and water in the obtained gel is 1: (1-3.5): (0.005-0.5): (0.1-1.0): (0.01-0.2): (15-50);
The molar ratio of metal ions to SiO 2 in the obtained gel is more than 0 and less than or equal to 0.05;
S2) heating and dynamically crystallizing the precursor gel obtained in the step S1), and washing, suction filtering, drying and roasting the obtained product to obtain the MWW structure molecular sieve; the MWW structure molecular sieve comprises an MCM-22 molecular sieve, an MCM-49 molecular sieve or an MCM-56 molecular sieve.
2. The method for producing 5-hydroxymethylfurfural according to claim 1, wherein in step S1), the silicon source is selected from one or more of white carbon black, an ammonia-type silica sol, a coarse pore silica gel, silicic acid and ethyl orthosilicate;
the aluminum source is selected from one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum oxide monohydrate.
3. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein in step S1), the metal complexing agent is selected from ethylenediamine and triethylamine.
4. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein in step S2), the temperature of the heating dynamic crystallization is 140 ℃ to 180 ℃, and the time of the heating dynamic crystallization is 48h to 144h.
5. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the mass ratio of glucose, organic solvent, sodium chloride, catalyst and water is (0.05-0.2): (4-10): (0.2-0.5): (0.01-0.03): (1-4).
6. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the temperature of the catalytic glucose conversion reaction is 160-200 ℃, and the time of the catalytic glucose conversion reaction is 0.25-8 h.
CN202311120889.2A 2023-08-31 2023-08-31 MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural Active CN117142486B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311120889.2A CN117142486B (en) 2023-08-31 2023-08-31 MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311120889.2A CN117142486B (en) 2023-08-31 2023-08-31 MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural

Publications (2)

Publication Number Publication Date
CN117142486A CN117142486A (en) 2023-12-01
CN117142486B true CN117142486B (en) 2024-05-10

Family

ID=88905657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311120889.2A Active CN117142486B (en) 2023-08-31 2023-08-31 MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural

Country Status (1)

Country Link
CN (1) CN117142486B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1353010A (en) * 2000-11-02 2002-06-12 中国石油化工股份有限公司 Molecular sieve containing heteroatoms and its synthesis
CN102092740A (en) * 2010-12-07 2011-06-15 哈尔滨师范大学 Method for directly preparing H-MCM-22 molecular sieve
CN104445255A (en) * 2014-12-04 2015-03-25 南京工业大学 Preparation method of heteroatom MCM-49 zeolite molecular sieve
CN104591203A (en) * 2013-10-31 2015-05-06 中国科学院大连化学物理研究所 MCM-22 molecular sieve solvothermal synthesis method and product thereof, and uses of MCM-22 molecular sieve
CN104709919A (en) * 2013-12-16 2015-06-17 中国科学院大连化学物理研究所 Tin-containing molecular sieve with MWW topological structure and preparation and application thereof
CN106517232A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 H-MCM-22 molecular sieve synthesis method and synthesized molecular sieve
CN108440463A (en) * 2018-05-24 2018-08-24 厦门大学 A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis
CN112158856A (en) * 2020-08-25 2021-01-01 郑州大学 Method for preparing Ti-MWW molecular sieve
CN114229868A (en) * 2022-01-13 2022-03-25 中国石油大学(北京) MWW molecular sieve, preparation method thereof and application of alkaloid in preparation of MWW molecular sieve
KR20230054174A (en) * 2021-10-15 2023-04-24 인천대학교 산학협력단 Manufacturing method of 2 dimensional mww type zeolite catalyst for conversion reaction of glucose and 2 dimensional mww type zeolite catalyst manufactured by the method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111763130B (en) * 2020-06-22 2023-01-03 南京克米斯璀新能源科技有限公司 Method for producing long-chain alkylbenzene

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1353010A (en) * 2000-11-02 2002-06-12 中国石油化工股份有限公司 Molecular sieve containing heteroatoms and its synthesis
CN102092740A (en) * 2010-12-07 2011-06-15 哈尔滨师范大学 Method for directly preparing H-MCM-22 molecular sieve
CN104591203A (en) * 2013-10-31 2015-05-06 中国科学院大连化学物理研究所 MCM-22 molecular sieve solvothermal synthesis method and product thereof, and uses of MCM-22 molecular sieve
CN104709919A (en) * 2013-12-16 2015-06-17 中国科学院大连化学物理研究所 Tin-containing molecular sieve with MWW topological structure and preparation and application thereof
CN104445255A (en) * 2014-12-04 2015-03-25 南京工业大学 Preparation method of heteroatom MCM-49 zeolite molecular sieve
CN106517232A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 H-MCM-22 molecular sieve synthesis method and synthesized molecular sieve
CN108440463A (en) * 2018-05-24 2018-08-24 厦门大学 A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis
CN112158856A (en) * 2020-08-25 2021-01-01 郑州大学 Method for preparing Ti-MWW molecular sieve
KR20230054174A (en) * 2021-10-15 2023-04-24 인천대학교 산학협력단 Manufacturing method of 2 dimensional mww type zeolite catalyst for conversion reaction of glucose and 2 dimensional mww type zeolite catalyst manufactured by the method
CN114229868A (en) * 2022-01-13 2022-03-25 中国石油大学(北京) MWW molecular sieve, preparation method thereof and application of alkaloid in preparation of MWW molecular sieve

Also Published As

Publication number Publication date
CN117142486A (en) 2023-12-01

Similar Documents

Publication Publication Date Title
CN108264057B (en) Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite
WO2020248695A1 (en) Alkali metal ion-modified titanium silicon molecular sieve ts-1 for gas phase epoxidation reaction of propylene and hydrogen peroxide, and preparation method therefor
CN104724720B (en) A kind of synthetic method of the molecular sieves of HZSM 5
CN102627287A (en) Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials
CN112774726B (en) Spherical titanium-silicon molecular sieve catalyst and preparation method thereof
CN109384246A (en) A kind of AEI structure molecular screen and its preparation method and application
CN107188194B (en) A method of preparing high catalytic activity Ti-MWW molecular sieve
CN109107526B (en) Method for synchronously synthesizing zeolite and LDH (layered double hydroxide) by taking fly ash as raw material
CN101723405A (en) Method for preparing ZSM-5 molecular sieves
CN111054425B (en) hydrotalcite/MCM-41 mesoporous silicon composite solid base catalyst and in-situ preparation method and application thereof
CN105197955A (en) Method for low-temperature solvent-free synthesis of high-silicon small-size Cu-SSZ-13 zeolite molecular sieve
CN114436279B (en) ZSM-22 molecular sieve, preparation method and application thereof, and n-dodecane isomerization reaction
CN108722488B (en) Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof
CN117142486B (en) MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural
CN104386706A (en) Method for synthesizing CHA-type molecular sieve by using zinc-amine complex as template agent
CN114105166B (en) Organic template agent, preparation method and application thereof, high-silicon KFI zeolite molecular sieve, preparation method and application thereof
CN108786867B (en) Preparation method and application of fluorine anion modified hydrotalcite-like catalyst
CN113694960B (en) ZrCu-MOR zeolite for synthesizing 5-ethoxymethyl furfural and preparation method thereof
CN111017942A (en) Seed crystal for synthesizing L-type molecular sieve and preparation method and application thereof
CN111422881B (en) TON type zeolite molecular sieve and preparation method thereof
CN109824631B (en) Application of copper-doped aluminum phosphate molecular sieve catalyst synthesized by ionothermal method in synthesis of 5-hydroxymethylfurfural
CN102373069A (en) Method used for C6-alkane cracking
CN113663721B (en) Preparation method and application of catalyst for preparing 1, 3-butadiene from ethanol
CN110745840A (en) ECR-1 zeolite, and preparation method and application thereof
AU2021105922A4 (en) ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant